US5004786A - Process for producing sulfomethylamide polymers - Google Patents
Process for producing sulfomethylamide polymers Download PDFInfo
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- US5004786A US5004786A US07/418,984 US41898489A US5004786A US 5004786 A US5004786 A US 5004786A US 41898489 A US41898489 A US 41898489A US 5004786 A US5004786 A US 5004786A
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- sulfomethylamide
- bisulfite
- formaldehyde
- reaction
- polyacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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- This invention relates broadly to the chemical arts, more particularly to the art of organic synthesis and specifically to the preparation of sulfomethylamide-containing polymers.
- an important object of the present invention is to provide sulfomethylpolyacrylamide and a method of synthesizing the same using formaldehyde and bisulfite.
- Another board object of the invention is to provide a simple, effective and inexpensive chemical route to sulfomethylacrylamide polymers and the like.
- sulfomethylamide-containing polymers are prepared from acrylamide-containing polymers with sodium formaldehyde bisulfite (or formaldehyde and sodium bisulfite) in from about 1/4 to about 8 hours at temperatures of at least about 100° C. and at a pH of less than 12, preferably at temperature higher than 110° C. and at a pH of 3 to 8. Under these reaction conditions, sulfomethylamide readily forms in high conversion, based on the sodium formaldehyde bisulfite charged.
- the products characterized by C-13 NMR spectroscopy, Infra-Red spectroscopy, and colloid titration, contain at least three functional groups: namely, carboxylate, primary amide and sulfomethylamide. Applicants have found that the elapsed time for completing the sulfomethylation is a product of such reaction kinetics as pH and temperature and not an independent variable.
- FIG. 1 is Carbon-13 Nuclear Magnetic Resonance spectrum of a solution of polyacrylamide and sodium formaldehyde bisulfite, at a pH of 12, after mixing;
- FIG. 2 is a similar spectrum after the solution was heated for 4 hours at 75° C.
- FIG. 3 is the Carbon-13 NMR spectrum for sulfomethylamide copolymer according to the present invention.
- polyacrylamide from the polymerization of acrylamide in an aqueous solution using redox initiators.
- Polymerizations conducted in a 28% solution produced polymer having an average molecular weight of 6000 as determined by GPC.
- the source of formaldehyde and bisulfite for the subsequent sulfomethylation reaction was selected to be 1:1 sodium formaldehyde bisulfite (hydroxymethanesulfonic acid, sodium salt) purchased from a commerical source. This latter material exhibited a sharp C-13 line at pH 6 and was employed without further purification.
- FIGS. 1 and 2 are Carbon-13 NMR spectra established by the aforementioned Dennis P. Bakalik for a solution of polyacrylamide and sodium formaldehyde bisulfite (1:0.5), at a pH of 12.
- the spectrum of FIG. 1 demonstrates that some reaction takes place rather quickly at ambient temperatures and high pH.
- the species principally responsible for the spectrum of FIG. 1 can be assigned and indicate the formation of a terpolymer of acrylamide, methylol acrylamide, and acrylate salt in addition to some low molecular weight species derived from formaldehyde, bisulfite and ammonia.
- the peak at 180.3 is due to the carbonyl of acrylamide in the terpolymer, while the bread peaks at 35.8 and 42.9 represent backbone carbons.
- the peaks at 177.9 and 64.4 are indicative of the carbonyl and methylene of methylol acrylamide units.
- the peak at 183.7 results from the acrylate carbonyl produced via hydrolysis.
- peaks present in the spectrum of FIG. 1 include those at 79.1, 78.1, 68.2 and 65.2.
- the board peak at 78.1 can be assigned to unreacted hydroxymethanesulfonate, through spiking experiments, while the peak at 65.2 represents the reaction product of ammonia with two moles of hydroxymethanesulfonate.
- FIG. 2 The spectrum of FIG. 2 was obtained after heating the reaction mixtures for 4 hours at 75° C. These are conditions that have been taught in the prior art as producing sulfomethylated polyacrylamide.
- the two major groupings of peaks in the carbonyl region at 180.5, 181.0 and 183.9, 184.4 are from arcylamide and acrylate carbonyls respectively. These pairs of peaks represent the major sequence triads generated on basic hydrolysis of polyacrylamide.
- the broad peaks at 35.8, 42.9, and 45.5 are due to backbone carbons of the copolymer.
- the spectrum of FIG. 3 representing a reaction product according to the present invention, exhibits an absence of peaks at 60.4, 65.3 and 69.7, representing the substituted amines.
- the spectrum of FIG. 3 is characterized by the occurrance of signals at 56.5 and 178.
- the 178 signal is consistent with the presence of a secondary amide.
- the 56.5 signal was determined to be a methylene from an off-resonance experiment. The broadness of this signal suggests it is a part of the polymer.
- the signal is assigned to the methylene between the nitrogen of the amide and the sulfur of the sulfonate.
- sulfonate is further confirmed by absorption bands at 1200 and 1050 cm 31 1 IR spectra of sulfomethylamide copolymer prepared according to the present invention at a pH of 5.5, and when acidified to a pH of 1.
- the presence of secondary amide is confirmed by an absorption band at 1550 cm 31 1 after the sample was acidified to pH 1 to remove carboxylate salt interference.
- the amount of sulfomethylamide group incorporated into the copolymers can be determined by photometric colloid titration at two pH's. The principle of this method is based on the fact that formaldehyde bisulfite will not be detected by this method. At a pH of 2-3, the carboxylic acid functionality will be negligibly ionized so that only the strong sulfonate group incorporated in the backbone will be determined by titration. At a pH of 10, since the carboxylic acid is completely ionized, both it and the sulfonate group will be titrated. The amount of sulfomethylamide incorporation determined by this method is in good agreement with that determined by the C-13 NMR method.
- sulfomethylpolyacrylamide is used herein to encompass the sulfomethylated homopolymers of acrylamide or their homologs and the sulfomethylated copolymers, including terpolymers, of acrylamide or their homologs, with acrylic acid or its homologs, the essential characteristic of the polyacrylamide moiety being the presence of a primary amide group.
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
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Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/418,984 US5004786A (en) | 1985-12-03 | 1989-10-06 | Process for producing sulfomethylamide polymers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80403685A | 1985-12-03 | 1985-12-03 | |
US07/004,841 US4762894A (en) | 1985-12-03 | 1987-01-12 | Sulfomethylamide-containing polymers |
US17944288A | 1988-04-08 | 1988-04-08 | |
US07/418,984 US5004786A (en) | 1985-12-03 | 1989-10-06 | Process for producing sulfomethylamide polymers |
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US17944288A Continuation | 1985-12-03 | 1988-04-08 |
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US5004786A true US5004786A (en) | 1991-04-02 |
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US07/418,984 Expired - Lifetime US5004786A (en) | 1985-12-03 | 1989-10-06 | Process for producing sulfomethylamide polymers |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5834294A (en) * | 1991-07-10 | 1998-11-10 | Newmont Gold Co. | Biooxidation process for recovery of metal values from sulfur-containing ore materials |
US6166165A (en) * | 1996-12-18 | 2000-12-26 | Witco Corporation | Polyurethane synthesis from functional group terminated polymers containing sulfonate groups |
US6383458B1 (en) | 1991-07-10 | 2002-05-07 | Newmont Mining Corporation | Biooxidation process for recovery of metal values from sulfur-containing ore materials |
US6482373B1 (en) | 1991-04-12 | 2002-11-19 | Newmont Usa Limited | Process for treating ore having recoverable metal values including arsenic containing components |
US6696283B1 (en) | 1991-07-10 | 2004-02-24 | Newmont Usa Limited | Particulate of sulfur-containing ore materials and heap made therefrom |
Citations (12)
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JPS4859664A (en) * | 1971-11-26 | 1973-08-21 | ||
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JPS5148154A (en) * | 1974-10-22 | 1976-04-24 | Tokyo Shibaura Electric Co | ZETSUENGATA KAIROBUHINNO SEIZOHOHO |
US4016086A (en) * | 1972-01-26 | 1977-04-05 | Marathon Oil Company | Polyacrylamide polymers derived from acrylonitrile without intermediate isolation |
JPS5274084A (en) * | 1975-12-15 | 1977-06-21 | Hamano Kogyo | Method of and agent for preventing migration of dye |
JPS53121091A (en) * | 1977-03-31 | 1978-10-23 | Sanyo Chem Ind Ltd | Production of modified carbamoyl polymer powder |
JPS5416593A (en) * | 1977-07-08 | 1979-02-07 | Nitto Chem Ind Co Ltd | Chemical modification of acryamide polymer |
JPS5444019A (en) * | 1977-09-14 | 1979-04-07 | Mitsubishi Chem Ind Ltd | Pesticide for plant viral disease |
JPS5516016A (en) * | 1978-07-18 | 1980-02-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Improved salt-resistant water-absorbing material |
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JPH0825983A (en) * | 1994-05-12 | 1996-01-30 | Kojima Press Co Ltd | Protective cover |
-
1989
- 1989-10-06 US US07/418,984 patent/US5004786A/en not_active Expired - Lifetime
Patent Citations (12)
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JPS4859664A (en) * | 1971-11-26 | 1973-08-21 | ||
US4016086A (en) * | 1972-01-26 | 1977-04-05 | Marathon Oil Company | Polyacrylamide polymers derived from acrylonitrile without intermediate isolation |
JPS4928111A (en) * | 1972-07-17 | 1974-03-13 | ||
JPS5148154A (en) * | 1974-10-22 | 1976-04-24 | Tokyo Shibaura Electric Co | ZETSUENGATA KAIROBUHINNO SEIZOHOHO |
JPS5274084A (en) * | 1975-12-15 | 1977-06-21 | Hamano Kogyo | Method of and agent for preventing migration of dye |
JPS53121091A (en) * | 1977-03-31 | 1978-10-23 | Sanyo Chem Ind Ltd | Production of modified carbamoyl polymer powder |
JPS5416593A (en) * | 1977-07-08 | 1979-02-07 | Nitto Chem Ind Co Ltd | Chemical modification of acryamide polymer |
DD151073A1 (en) * | 1977-08-15 | 1981-09-30 | Frank Wittig | METHOD FOR MODIFYING POLYMERS |
JPS5444019A (en) * | 1977-09-14 | 1979-04-07 | Mitsubishi Chem Ind Ltd | Pesticide for plant viral disease |
JPS5516016A (en) * | 1978-07-18 | 1980-02-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Improved salt-resistant water-absorbing material |
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JPH0825983A (en) * | 1994-05-12 | 1996-01-30 | Kojima Press Co Ltd | Protective cover |
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Author: B. Jansan, G. Ellinghorst; Title: Radiation Initiated Grafting of Hydrophillic & Reactive . . . ; Radiation Physical Chemistry, vol. 18, No. 5 6, pp. 1195 1102, 1981. * |
Author: Kh. Verani, I. Mladenov and M. Pundeva; Title: "Amination of Polyacrylonitrile Hydrolysate by the Hoffman Reaction"; Yearbook of the Institute of Chemical Technology--Bougas, vol. 10, 1973. |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6482373B1 (en) | 1991-04-12 | 2002-11-19 | Newmont Usa Limited | Process for treating ore having recoverable metal values including arsenic containing components |
US5834294A (en) * | 1991-07-10 | 1998-11-10 | Newmont Gold Co. | Biooxidation process for recovery of metal values from sulfur-containing ore materials |
US6383458B1 (en) | 1991-07-10 | 2002-05-07 | Newmont Mining Corporation | Biooxidation process for recovery of metal values from sulfur-containing ore materials |
US6696283B1 (en) | 1991-07-10 | 2004-02-24 | Newmont Usa Limited | Particulate of sulfur-containing ore materials and heap made therefrom |
US6166165A (en) * | 1996-12-18 | 2000-12-26 | Witco Corporation | Polyurethane synthesis from functional group terminated polymers containing sulfonate groups |
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